US20220073713A1 - Tread for a tire - Google Patents

Tread for a tire Download PDF

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Publication number
US20220073713A1
US20220073713A1 US17/416,654 US201917416654A US2022073713A1 US 20220073713 A1 US20220073713 A1 US 20220073713A1 US 201917416654 A US201917416654 A US 201917416654A US 2022073713 A1 US2022073713 A1 US 2022073713A1
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United States
Prior art keywords
tread
copolymer
rubber composition
tire according
lateral portions
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US17/416,654
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English (en)
Inventor
Jose Merino Lopez
Jose Carlos Araujo Da Silva
Aurore Crochet
Guillaume Hennebert
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Compagnie Generale des Etablissements Michelin SCA
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Compagnie Generale des Etablissements Michelin SCA
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Assigned to COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN reassignment COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ARAUJO DA SILVA, JOSE CARLOS, CROCHET, Aurore, HENNEBERT, GUILLAUME, MERINO LOPEZ, JOSE
Publication of US20220073713A1 publication Critical patent/US20220073713A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
    • B60C11/0041—Tyre tread bands; Tread patterns; Anti-skid inserts comprising different tread rubber layers
    • B60C11/005—Tyre tread bands; Tread patterns; Anti-skid inserts comprising different tread rubber layers with cap and base layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
    • B60C11/0041—Tyre tread bands; Tread patterns; Anti-skid inserts comprising different tread rubber layers
    • B60C11/005—Tyre tread bands; Tread patterns; Anti-skid inserts comprising different tread rubber layers with cap and base layers
    • B60C11/0058—Tyre tread bands; Tread patterns; Anti-skid inserts comprising different tread rubber layers with cap and base layers with different cap rubber layers in the axial direction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
    • B60C11/03—Tread patterns
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/083—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic polyenes, i.e. containing two or more carbon-to-carbon double bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
    • B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread rubber
    • B60C2011/0016—Physical properties or dimensions
    • B60C2011/0025—Modulus or tan delta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
    • B60C11/03—Tread patterns
    • B60C2011/0337—Tread patterns characterised by particular design features of the pattern
    • B60C2011/0339—Grooves
    • B60C2011/0341—Circumferential grooves

Definitions

  • the subject of the present invention is a vehicle tyre and, in particular, the tread of a vehicle tyre.
  • a tyre Since a tyre has a geometry exhibiting symmetry of revolution about an axis of rotation, the geometry of the tyre is generally described in a meridian plane containing the axis of rotation of the tyre.
  • the radial, axial and circumferential directions denote the directions perpendicular to the axis of rotation of the tyre, parallel to the axis of rotation of the tyre and perpendicular to the meridian plane, respectively.
  • the expressions “radially”, “axially” and “circumferentially” mean “in the radial direction”, “in the axial direction” and “in the circumferential direction”, respectively.
  • “Radially inner and radially outer, respectively” is understood to mean “closer to and further away from the axis of rotation of the tyre, respectively”. “Axially inner and axially outer, respectively” is understood to mean “closer to and further away from the equatorial plane of the tyre, respectively”, the equatorial plane of the tyre being the plane EP which passes through the middle of the tread surface of the tyre and is perpendicular to the axis of rotation of the tyre.
  • the tread is the part of the tyre intended to come into contact with the ground via a tread surface, and extending radially from a bottom surface to the tread surface, axially from a first tread edge to a second tread edge defining the axial width of the tread, and circumferentially over the whole periphery of the tyre.
  • the tread regardless of whether the tyre is intended to be fitted on a passenger vehicle or a heavy-duty vehicle, is provided with a tread pattern comprising, notably, tread pattern elements or elementary blocks delimited by various main, longitudinal or circumferential, transverse or oblique grooves, the elementary blocks also being able to have various finer slits or sipes.
  • the grooves form channels for draining off water when running on wet ground.
  • a radial-type tyre comprises a reinforcement, consisting of a crown reinforcement and a radial carcass reinforcement radially inside the crown reinforcement.
  • the crown reinforcement comprises at least one crown layer consisting of reinforcing elements or reinforcers coated with a rubber mixture and parallel to one another.
  • the radial carcass reinforcement comprises at least one carcass layer consisting of reinforcers coated with a rubber mixture, parallel to one another and oriented substantially radially, that is to say forming, with the circumferential direction, an angle of between 85° and 95°.
  • the rubber compositions of tyre treads are adapted for performance in terms of contact with a ground on which they are running, this being up to the regulatory wear of the tyres.
  • the tread of a tyre is responsible for a large part of the rolling resistance of that tyre. This contribution is of course very variable depending on the design of the tyre, but an order of magnitude of about 50% can be achieved.
  • one solution also consists in creating a stiffness gradient by a phenomenon of accommodation of the rubber composition of the tread as described in patent applications WO 02/10269 and WO 2012/084599.
  • This accommodation phenomenon results in the ability of the rubber composition to become less stiff at the surface of the tread under the effect of the deformations undergone by the tread during the rolling of the tyre.
  • This decrease in stiffness at the surface of the tread does not occur or occurs very little inside the tread, which thus maintains a higher level of stiffness than the surface of the tread.
  • a rubber composition comprising a copolymer of ethylene and of 1,3-butadiene, the processability of which is improved by the introduction of 5 to 10 phr of a plasticizing resin, is described in patent application JP 2013-185048. Not only is the molar content of ethylene in the copolymer much less than 50%, but the grip performance is also not addressed.
  • One subject of the invention is a tyre having an axis of rotation and a median plane perpendicular to the axis of rotation, and comprising two beads, two sidewalls connected to the beads, a crown connected to the ends of the two sidewalls with a crown reinforcement, and a radially outer rubber tread, the tread being axially separated into three portions, a central portion and two lateral portions.
  • This tyre is characterized in that the rubber composition of the lateral portions comprises more than 50 phr of a copolymer of ethylene and of a 1,3-diene, a reinforcing filler and a plasticizing system, the 1,3-diene being 1,3-butadiene or isoprene and the ethylene units in the copolymer representing more than 50 mol % of all the monomer units of the copolymer.
  • the particular rubber composition of the two lateral portions makes it possible to improve the wear resistance of the tyre and in particular the wear pattern on the shoulders of the tyre. It also makes it possible to reduce the rolling resistance of the tyre during running.
  • the tread comprising a plurality of tread pattern elements with lateral faces and a contact face intended to come into contact with the roadway when the tyre is running and a plurality of circumferential grooves each delimited by lateral faces of adjacent tread pattern elements that face one another, and delimited by a base, the central portion extends axially on either side of the median plane of the tyre beyond the plurality of circumferential grooves, and in which said central portion includes the bases of said circumferential grooves.
  • the tread comprising a plurality of tread pattern elements with lateral faces and a contact face intended to come into contact with the roadway when the tyre is running and a plurality of circumferential grooves each delimited by lateral faces of adjacent tread pattern elements that face one another, and delimited by a base, the central portion extends axially to the axially outermost circumferential groove, at least on one side of the median plane of the tyre and preferably on either side of the median plane of the tyre.
  • the tread comprising a radially inner first layer C 1 and a radially outer second layer C 2 , the lateral portions of the first layer C 1 constitute the lateral portions and the second layer C 2 constitutes the central portion of the tread.
  • the rubber composition of the lateral portions of the tread may comprise a second elastomer, preferably a diene elastomer, that is to say comprising diene monomer units.
  • the content of the second elastomer is preferably less than 30 phr and very preferentially less than 10 phr.
  • the second elastomer can be a highly unsaturated diene elastomer selected from the group consisting of polybutadienes, polyisoprenes, butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
  • the copolymer of ethylene and of a 1,3-diene is the only elastomer of the rubber composition of the lateral portions of the tread.
  • the rubber composition of the central portion of the tread comprises less than 50 phr of a copolymer of ethylene and of a 1,3-diene, a reinforcing filler and a plasticizing system, the 1,3-diene being 1,3-butadiene or isoprene and the ethylene units in the copolymer representing more than 50 mol % of all the monomer units of the copolymer.
  • the ratio K between the dynamic shear modulus of the rubber composition of the lateral portions of the tread and the dynamic shear modulus of the rubber composition of the central portion of the tread is greater than 1.1 and preferably greater than 1.2, the dynamic shear moduli being measured at 60° C. during a temperature sweep at an imposed stress of 0.7 MPa and at a frequency of 10 Hz.
  • This ratio of moduli between the lateral portions and the central portion of the tread enables the lateral portions to stiffen the tread and the crown of the tyre. This improves the handling of the tyre.
  • K is less than 2.5 and very preferentially less than or equal to 1.5.
  • the dynamic shear modulus of the lateral portions is preferably between 1 and 2.5 MPa.
  • the grip performance of the tyre may be reduced.
  • FIG. 1 very schematically shows (without being drawn to any particular scale) a radial cross section through the crown of a tyre in accordance with one embodiment of the invention
  • FIG. 2 shows an embodiment variant of the tyre crown from FIG. 1 ;
  • FIG. 3 shows another embodiment of a tyre crown according to the invention.
  • FIG. 1 schematically shows a radial cross section through the crown 2 of a pneumatic tyre or tyre 1 according to one embodiment of the invention.
  • FIG. 1 also indicates the axial X, circumferential C and radial Z directions and also the median plane EP (plane perpendicular to the axis of rotation of the tyre which is situated halfway between the two beads and passes through the middle of the crown reinforcement of the tyre).
  • This tyre 1 comprises a crown 2 reinforced by a crown reinforcement or belt 3 , two sidewalls (not shown) and two beads (not shown), each of these beads being reinforced with a bead wire (not shown).
  • the crown reinforcement 3 is surmounted radially externally by a rubber tread 7 .
  • a carcass reinforcement 4 is positioned radially inside the crown reinforcement 3 , is anchored in each bead and extends from one bead to the other.
  • the carcass reinforcement 4 is made up of at least one ply reinforced by what are known as “radial” cords, for example of textile or metal, that is to say that these cords are disposed virtually parallel to one another and extend from one bead to the other so as to form an angle of between 80° and 90° with the median circumferential plane EP.
  • a airtight layer 5 extends from one bead to the other radially on the inside with respect to the carcass reinforcement 4 .
  • the cross section from FIG. 1 of the tread 6 illustrates five tread pattern elements, three in the central portion of the crown, the centre tread pattern elements 7 and two axially laterally, at the shoulders of the crown, the shoulder tread pattern elements 8 .
  • Each groove has two opposite lateral faces 9 of the adjacent tread pattern elements and also a groove base 12 .
  • the central portion 15 of the tread extends axially on either side of the median plane EP beyond the circumferential grooves 11 .
  • the two lateral portions 16 of the tread 6 therefore constitute the axially outer portions of the two shoulder tread pattern elements 8 .
  • the axial width of the shoulder tread pattern element 8 is Lep.
  • the axial width on the contact face 10 of the shoulder tread pattern element 8 when new is d.
  • the d/Lep ratio is greater than 1 ⁇ 3.
  • shoulder tread pattern element 8 a this ratio increases with the wear of the tread.
  • shoulder tread pattern element 8 b the partition between the central portion and the lateral portion is such that it moves closer to the median plane when it moves radially away from the axis of rotation. This variant makes it possible to maintain a shear stiffness of the shoulder tread pattern element 8 b which is substantially constant as the tread wears.
  • the central portion of the tread extends axially to the axially outermost circumferential grooves 11 , on either side of the median plane EP of the tyre.
  • it is the whole of the shoulder tread pattern elements 8 which constitutes the lateral portions of the tread.
  • the base of the grooves it is advantageous for the base of the grooves to be part of the central portion of the tread because the rubber composition of the central portion has a lower dynamic stiffness than that of the lateral portions and the moulding of the bases of the grooves is more robust. This is what is illustrated in FIG. 2 .
  • the tread comprises a radially inner first layer C 1 and a radially outer second layer C 2 .
  • the first layer C 1 is continuous from the tread pattern element 8 a to the tread pattern element 8 b over the entire axial width of the tread.
  • the lateral portions of the first layer C 1 constitute the lateral portions 16 and the second layer C 2 constitutes the central portion 15 of the tread.
  • FIGS. 1 to 3 clearly illustrate the role of stiffening the tread and the crown of the tyre when the dynamic modulus ratio between the two rubber mixtures of the lateral portions and of the central portion is greater than 1.1 and preferably greater than 1.2. It is preferable not to exceed a ratio of 2.5, and very preferentially 1.5, so as not to degrade the grip of the tyre when the tread surface is due in large part to the lateral portions.
  • any interval of values denoted by the expression “between a and b” represents the range of values greater than “a” and less than “b” (that is to say limits a and b excluded), whereas any interval of values denoted by the expression “from a to b” means the range of values extending from “a” up to “b” (that is to say including the strict limits a and b).
  • the abbreviation “phr” means parts by weight per hundred parts by weight of elastomer (of the total of the elastomers if several elastomers are present).
  • the expression “all of the monomer units of the elastomer” or “the total amount of the monomer units of the elastomer” means all the constituent repeating units of the elastomer which result from the insertion of the monomers into the elastomer chain by polymerization. Unless otherwise indicated, the contents of a monomer unit or repeating unit in the highly saturated diene elastomer are given as molar percentages calculated on the basis of the monomer units of the copolymer, that is to say on the basis of all of the monomer units of the elastomer.
  • the compounds mentioned in the description may be of fossil or biobased origin. In the latter case, they can result, partially or completely, from biomass or be obtained from renewable starting materials resulting from biomass. Elastomers, plasticizers, fillers and the like are notably concerned.
  • the copolymer of ethylene and of 1,3-diene which is useful for the purposes of the invention is a preferably random elastomer which comprises ethylene units resulting from the polymerization of ethylene.
  • ethylene unit refers to the —(CH 2 —CH 2 )— unit resulting from the insertion of ethylene into the elastomer chain.
  • the ethylene units represent more than 50 mol % of the monomer units of the copolymer.
  • the ethylene units in the copolymer represent more than 60 mol %, advantageously more than 70 mol % of the monomer units of the copolymer.
  • the highly saturated diene elastomer preferentially comprises at most 90 mol % of ethylene unit.
  • the copolymer which is useful for the purposes of the invention also referred to below under the name “highly saturated diene elastomer”, also comprises 1,3-diene units resulting from the polymerization of a 1,3-diene, the 1,3-diene being 1,3-butadiene or isoprene.
  • 1,3-diene unit refers to units resulting from the insertion of the 1,3-diene via a 1,4 addition, a 1,2 addition or a 3,4 addition in the case of isoprene.
  • the 1,3-diene is 1,3-butadiene.
  • the copolymer of ethylene and of a 1,3-diene contains units of formula (I).
  • the presence of a saturated 6-membered cyclic unit, 1,2-cyclohexanediyl, of formula (I) as a monomer unit in the copolymer can result from a series of very particular insertions of ethylene and 1,3-butadiene in the polymer chain during its growth.
  • the copolymer of ethylene and of a 1,3-diene contains units of formula (II-1) or (II-2).
  • the copolymer of ethylene and of a 1,3-diene contains units of formula (I) and of formula (II-1).
  • the highly saturated diene elastomer is devoid of units of formula (I).
  • the copolymer of ethylene and of a 1,3-diene preferably contains units of formula (II-1) or (II-2).
  • the highly saturated diene elastomer contains units resulting from the insertion of the 1,3-diene by a 1,4 addition, that is to say units of formula —CH 2 —CH ⁇ CH—CH 2 — when the 1,3-diene is 1,3-butadiene, or of formula —CH 2 —CMe ⁇ C—CH 2 — when the 1,3-diene is isoprene.
  • the highly saturated diene elastomer comprises units of formula (I) or units of formula (II-1) or else comprises units of formula (I) and units of formula (II-1)
  • the molar percentages of units of formula (I) and of units of formula (II-1) in the highly saturated diene elastomer, respectively o and p preferably satisfy the following equation (eq. 1), more preferentially the equation (eq. 2), o and p being calculated on the basis of all the monomer units of the highly saturated diene elastomer.
  • the highly saturated diene elastomer is preferentially a random copolymer.
  • the highly saturated diene elastomer in particular according to the first embodiment, according to the second embodiment, according to the third embodiment and according to the fourth embodiment, can be obtained according to various synthesis methods known to those skilled in the art, in particular as a function of the intended microstructure of the highly saturated diene elastomer. Generally, it may be prepared by copolymerization at least of a 1,3-diene, preferably 1,3-butadiene, and of ethylene and according to known synthesis methods, in particular in the presence of a catalytic system comprising a metallocene complex.
  • catalytic systems based on metallocene complexes, which catalytic systems are described in documents EP 1 092 731, WO 2004/035639, WO 2007/054223 and WO 2007/054224 in the name of the applicant.
  • the highly saturated diene elastomer including the case when it is random, may also be prepared via a process using a catalytic system of preformed type such as those described in documents WO 2017/093654 A1, WO 2018/020122 A1 and WO 2018/020123 A1.
  • the highly saturated diene elastomer may consist of a mixture of copolymers of ethylene and of 1,3-diene which differ from each other by virtue of their microstructures or their macrostructures.
  • the highly saturated diene elastomer is preferably a copolymer of ethylene and of 1,3-butadiene, more preferentially a random copolymer of ethylene and of 1,3-butadiene.
  • the copolymer of ethylene and of a 1,3-diene bears at the chain end a functional group F1 which is a silanol or alkoxysilane function.
  • F1 which is a silanol or alkoxysilane function.
  • the silanol or alkoxysilane function is located at the end of the chain of the highly saturated diene elastomer.
  • the alkoxysilane or silanol function borne at one of the ends is referred to in the present application by the name the functional group F1.
  • it is attached directly via a covalent bond to the terminal unit of the highly saturated diene elastomer, which means to say that the silicon atom of the function is directly bonded, covalently, to a carbon atom of the terminal unit of the highly saturated diene elastomer.
  • the terminal unit to which the functional group F1 is directly attached preferably consists of a methylene bonded to an ethylene unit or to a 1,2-cyclohexanediyl unit, of formula (I), the Si atom being bonded to the methylene.
  • a terminal unit is understood to mean the last unit inserted in the copolymer chain by copolymerization, which unit is preceded by the penultimate unit, which is itself preceded by the antepenultimate unit.
  • the functional group F1 is of formula (III-a)
  • the R1 symbols which may be identical or different, representing an alkyl
  • the R2 symbols which may be identical or different, representing a hydrogen atom, a hydrocarbon chain or a hydrocarbon chain substituted by a chemical function F2; f being an integer ranging from 0 to 2.
  • the R1 symbols are preferentially an alkyl having at most 6 carbon atoms, more preferentially a methyl or an ethyl, more preferentially still a methyl.
  • the R1 symbols are advantageously identical, in particular methyl or ethyl, more particularly methyl.
  • the functional group F1 is of formula (III-b)
  • R2 symbols which may be identical or different, representing a hydrogen atom, a hydrocarbon chain or a hydrocarbon chain substituted by a chemical function F2.
  • alkyls in particular those having 1 to 6 carbon atoms, preferentially methyl or ethyl, more preferentially methyl.
  • alkanediyl chains in particular those comprising at most 6 carbon atoms, very particularly the 1,3-propanediyl group, the alkanediyl group bearing a substituent, the chemical function F2, in other words one valence of the alkanediyl chain for the function F2, the other valence for the silicon atom of the silanol or alkoxysilane function.
  • a chemical function F2 is understood to mean a group which is different from a saturated hydrocarbon group and which may participate in chemical reactions.
  • the chemical functions which may be suitable mention may be made of the ether function, the thioether function, the primary, secondary or tertiary amine function, the thiol function, the silyl function.
  • the primary or secondary amine or thiol functions may be protected or may not be protected.
  • the protective group for the amine and thiol functions is for example a silyl group, in particular a trimethylsilyl or tert-butyldimethylsilyl group.
  • the chemical function F2 is a primary, secondary or tertiary amine function or a thiol function, the primary or secondary amine or thiol function being protected by a protecting group or being unprotected.
  • the R2 symbols which may be identical or different, represent an alkyl having at most 6 carbon atoms or an alkanediyl chain having at most 6 carbon atoms and substituted by a chemical function F2 in formulae (III-a) and (III-b).
  • the dimethylsilanol, diethylsilanol, 3-(N,N-dimethylamino)propylmethylsilanol, 3-(N,N-dimethylamino)propylethylsilanol, 3-aminopropylmethylsilanol, 3-aminopropylethylsilanol, 3-thiopropylethylsilanol and 3-thiopropylmethylsilanol groups are suitable.
  • functional group F1 Mention may also be made, as functional group F1, of the functional groups whether they are in the alkoxy or silanol form, which have been mentioned above and which comprise an amine or thiol function in a form protected by a silyl group, in particular trimethylsilyl or tert-butyldimethylsilyl group.
  • the functional group F1 is of formula (III-a) in which f is equal to 1.
  • the groups for which R1 is a methyl or an ethyl such as for example the dimethoxymethylsilyl, dimethoxyethylsilyl, diethoxymethylsilyl, diethoxyethylsilyl, 3-(N,N-dimethylamino)propyldimethoxysilyl, 3-(N,N-dimethylamino)propyldiethoxysilyl, 3-aminopropyldimethoxysilyl, 3-aminopropyldiethoxysilyl, 3-thiopropyldimethoxysilyl and 3-thiopropyldiethoxysilyl groups, are very particularly suitable.
  • the protected forms of the amine or thiol function of the last 4 functional groups mentioned in the preceding list protected by a silyl group, in particular trimethylsilyl or tert-
  • the functional group F1 is of formula (III-a) in which f is equal to 1 and R1 is a methyl.
  • copolymer of ethylene and of a 1,3-diene which bears at the chain end a functional group F1, silanol or alkoxysilane function, can be prepared by the process described in the patent application filed under number PCT/FR2018/051305 or in the patent application filed under number PCT/FR2018/051306, which process comprises steps (a) and (b), and where appropriate, step (c) below:
  • step (b) the reaction of a functionalizing agent with the polymer obtained in step (a);
  • Step (a) is common to the copolymerization step carried out to prepare the non-functional homologous copolymers described above, with the only difference being that the copolymerization reaction is followed by a reaction for functionalization of the copolymer, step (b).
  • Step (b) consists in reacting a functionalizing agent with the copolymer obtained in step (a) in order to functionalize the copolymer at the chain end.
  • the functionalizing agent is a compound of formula (IV),
  • the alkoxy group is preferably methoxy or ethoxy.
  • the Fc1 symbol represents a halogen atom
  • the halogen atom is preferably chlorine.
  • the alkoxy group is preferably methoxy or ethoxy.
  • the Fc1 symbol represents a halogen atom
  • the halogen atom is preferably chlorine.
  • the functionalizing agent can be of formula (IV-1), of formula (IV-2), of formula (IV-3) or of formula (IV-4),
  • alkyls preferably alkyls having at most 6 carbon atoms, more preferentially methyl or ethyl, better still methyl.
  • hydrocarbon chains substituted by a chemical function Fc2 which are represented by the Rc2 symbols in formulae (IV), (IV-1), (IV-2), (IV-3) and (IV-4), mention may be made of alkanediyl chains, preferably those comprising at most 6 carbon atoms, more preferentially the 1,3-propanediyl group, the alkanediyl group bearing a substituent, the chemical function Fc2, in other words one valence of the alkanediyl chain for the function F2, the other valence for the silicon atom of the silanol or alkoxysilane function.
  • a chemical function is understood to mean a group which is different from a saturated hydrocarbon group and which may participate in chemical reactions.
  • the chemical function Fc2 is a group that is chemically inert with respect to the chemical species present in the polymerization medium.
  • the chemical function Fc2 may be in a protected form, such as for example in the case of the primary amine, secondary amine or thiol function. Mention may be made, as chemical function Fc2, of the ether, thioether, protected primary amine, protected secondary amine, tertiary amine, protected thiol, and silyl functions.
  • the chemical function Fc2 is a protected primary amine function, a protected secondary amine function, a tertiary amine function or a protected thiol function.
  • protective groups for the primary amine, secondary amine and thiol functions mention may be made of silyl groups, for example the trimethylsilyl and tert-butyldimethylsilyl groups.
  • g is preferably other than 0, which means that the functionalizing agent comprises at least one Si—Rc2 bond.
  • the functionalizing agent is typically added to the polymerization medium resulting from step (a). It is typically added to the polymerization medium at a degree of conversion of the monomers chosen by a person skilled in the art depending on the desired macrostructure of the elastomer. Since step (a) is generally carried out under ethylene pressure, a degassing of the polymerization reactor may be carried out before the addition of the functionalizing agent.
  • the functionalizing agent is added under inert and anhydrous conditions to the polymerization medium, maintained at the polymerization temperature. Use is typically made of from 0.25 to 10 mol of functionalizing agent per 1 mol of cocatalyst, preferably of from 2 to 4 mol of functionalizing agent per 1 mol of cocatalyst.
  • the functionalizing agent is bought into contact with the polymerization medium for a time sufficient to enable the functionalization reaction.
  • This contact time is judiciously chosen by a person skilled in the art as a function of the concentration of the reaction medium and of the temperature of the reaction medium.
  • the functionalization reaction is carried out under stirring, at a temperature ranging from 17° C. to 80° C., for 0.01 to 24 hours.
  • the elastomer may be recovered, in particular by isolating it from the reaction medium.
  • the techniques for separating the elastomer from the reaction medium are well known to a person skilled in the art and are chosen by a person skilled in the art depending on the amount of elastomer to be separated, its macrostructure and the tools available to a person skilled in the art. Mention may be made, for example, of the techniques of coagulating the elastomer in a solvent such as methanol, the techniques of evaporating the solvent of the reaction medium and the residual monomers, for example under reduced pressure.
  • step (b) may be followed by a hydrolysis reaction in order to form an elastomer bearing a silanol function at the chain end.
  • the hydrolysis may be carried out by a step of stripping of the solution containing the elastomer at the end of step (b), in a manner known to a person skilled in the art.
  • step (b) may also be followed by a hydrolysis reaction in order to deprotect the function at the end of the chain of the elastomer.
  • the hydrolysis reaction, step of deprotecting the function is generally carried out in an acid or basic medium depending on the chemical nature of the function to be deprotected.
  • a silyl group in particular trimethylsilyl or tert-butyldimethylsilyl group, which protects an amine or thiol function may be hydrolysed in an acid or basic medium in a manner known to a person skilled in the art.
  • the choice of the deprotection conditions is judiciously made by a person skilled in the art taking into account the chemical structure of the substrate to be deprotected.
  • Step (c) is an optional step depending on whether or not it is desired to convert the functional group into a silanol function or whether or not it is desired to deprotect the protected function.
  • step (c) is carried out before separating the elastomer from the reaction medium at the end of step (b) or else at the same time as this separation step.
  • the content of the copolymer of ethylene and of a 1,3-diene is greater than 50 phr, preferentially greater than 70 phr.
  • the remainder to 100 phr can be any diene elastomer, for example a 1,3-butadiene homopolymer or copolymer or else an isoprene homopolymer or copolymer.
  • the content of the copolymer of ethylene and of a 1,3-diene is 100 phr.
  • a high content of the copolymer in the rubber composition is even more favourable for the performance compromise between rolling resistance, wear resistance and grip.
  • the rubber composition of the lateral portions comprises a reinforcing filler and a plasticizing system.
  • the plasticizing system is preferably hydrocarbon-based.
  • the reinforcing filler comprises a silica.
  • a reinforcing filler typically consists of nanoparticles of which the mean (weight-average) size is less than a micrometre, generally less than 500 nm, usually between 20 and 200 nm, in particular and more preferentially between 20 and 150 nm.
  • the content of reinforcing filler in the rubber composition of the lateral portions is advantageously greater than or equal to 35 phr and less than or equal to 100 phr, preferably greater than or equal to 50 phr and less than or equal to 100 phr.
  • the silica represents more than 50% by weight of the reinforcing filler. More preferentially, the silica represents more than 85% by weight of the reinforcing filler.
  • the silica used can be any reinforcing silica known to a person skilled in the art, in particular any precipitated or fumed silica exhibiting a BET specific surface area and a CTAB specific surface area both of less than 450 m 2 /g, preferably within a range extending from 30 to 400 m 2 /g, in particular from 60 to 300 m 2 /g.
  • the BET specific surface area is determined by gas adsorption using the Brunauer-Emmett-Teller method described in “The Journal of the American Chemical Society”, (Vol.
  • CTAB specific surface area values were determined according to the standard NF ISO 5794-1, appendix G of June 2010. The process is based on the adsorption of CTAB (N-hexadecyl-N,N,N-trimethylammonium bromide) on the “external” surface of the reinforcing filler.
  • any type of precipitated silica in particular highly dispersible precipitated silicas (referred to as “HDS” for “highly dispersible” or “highly dispersible silica”), can be used.
  • HDS highly dispersible precipitated silicas
  • These precipitated silicas which may or may not be highly dispersible, are well known to those skilled in the art. Mention may be made, for example, of the silicas described in applications WO 03/016215-A1 and WO 03/016387-A1.
  • Use may in particular be made, among commercial HDS silicas, of the Ultrasil® 5000GR and Ultrasil® 7000GR silicas from Evonik or the Zeosil® 1085GR, Zeosil® 1115 MP, Zeosil® 1165MP, Zeosil® Premium 200MP and Zeosil® HRS 1200 MP silicas from Solvay.
  • Non-HDS silicas Use may be made, as non-HDS silicas, of the following commercial silicas: the Ultrasil® VN2GR and Ultrasil® VN3GR silicas from Evonik, the Zeosil® 175GR silica from Solvay or the Hi-Sil EZ120G(-D), Hi-Sil EZ160G(-D), Hi-Sil EZ200G(-D), Hi-Sil 243LD, Hi-Sil 210 and Hi-Sil HDP 320G silicas from PPG.
  • the reinforcing filler may comprise any type of “reinforcing” filler other than silica, known for its capacity to reinforce a rubber composition which can be used in particular for the manufacture of tyres, for example a carbon black.
  • All carbon blacks in particular the blacks conventionally used in tyres or their treads, are suitable as carbon blacks.
  • These carbon blacks can be used in the isolated state, as available commercially, or in any other form, for example as support for some of the rubber additives used.
  • the carbon black is used at a content of less than or equal to 20 phr, more preferentially less than or equal to 10 phr (for example the carbon black content may be in a range extending from 0.5 to 20 phr, in particular extending from 1 to 10 phr).
  • the carbon black content in the rubber composition is less than or equal to 5 phr.
  • the colouring properties (black pigmenting agent) and UV-stabilizing properties of the carbon blacks are beneficial, without, moreover, adversely affecting the typical performance qualities contributed by the silica.
  • an at least bifunctional coupling agent intended to ensure a sufficient connection, of chemical and/or physical nature, between the inorganic filler (surface of its particles) and the elastomer, in which case the rubber composition of the lateral portions comprises a coupling agent for binding the silica to the elastomer.
  • an at least bifunctional coupling agent intended to ensure a sufficient connection, of chemical and/or physical nature, between the inorganic filler (surface of its particles) and the elastomer, in which case the rubber composition of the lateral portions comprises a coupling agent for binding the silica to the elastomer.
  • Use is made in particular of organosilanes or polyorganosiloxanes which are at least bifunctional.
  • the term “bifunctional” is understood to mean a compound having a first functional group capable of interacting with the inorganic filler and a second functional group capable of interacting with the elastomer.
  • silane polysulfides referred to as “symmetrical” or “asymmetrical” depending on their specific structure, as described, for example, in applications WO 03/002648-A1 (or US 2005/016651-A1) and WO 03/002649-A1 (or US 2005/016650-A1).
  • silane polysulfides corresponding to general formula (V) below:
  • the mean value of the “x” indices is a fractional number preferably within a range extending from 2 to 5, more preferentially of approximately 4.
  • silane polysulfides of bis((C 1 -C 4 )alkoxyl(C 1 -C 4 )alkylsilyl(C 1 -C 4 )alkyl) polysulfides (in particular disulfides, trisulfides or tetrasulfides), such as, for example, bis(3-trimethoxysilylpropyl) or bis(3-triethoxysilylpropyl) polysulfides.
  • TESPT bis(3-triethoxysilylpropyl) tetrasulfide
  • TESPD bis(triethoxysilylpropyl) disulfide
  • Si75 bis(triethoxysilylpropyl) disulfide
  • the content of coupling agent in the rubber composition of the lateral portions is advantageously less than or equal to 25 phr, it being understood that it is generally desirable to use as little as possible thereof.
  • the content of coupling agent represents from 0.5% to 15% by weight, with respect to the amount of reinforcing inorganic filler. Its content is preferentially within a range extending from 0.5 to 20 phr, more preferentially within a range extending from 3 to 15 phr. This content is easily adjusted by a person skilled in the art according to the content of reinforcing inorganic filler used in the composition of the lateral portions of the tread of the tyre of the invention.
  • This plasticizing system advantageously comprises a hydrocarbon plasticizing resin and a hydrocarbon liquid plasticizing agent, it being understood that the total content of hydrocarbon plasticizing resin and hydrocarbon liquid plasticizing agent is greater than 10 phr and less than or equal to 80 phr, preferably greater than or equal to equal to 30 phr and less than or equal to 80 phr.
  • Hydrocarbon resins also known as hydrocarbon plasticizing resins, are polymers well known to those skilled in the art, essentially based on carbon and hydrogen but which can comprise other types of atoms, for example oxygen, which can be used in particular as plasticizing agents or tackifying agents in polymer matrices. They are by nature at least partially miscible (i.e. compatible) at the contents used with the polymer compositions for which they are intended, so as to act as true diluents. They have been described, for example, in the book entitled “Hydrocarbon Resins” by R. Mildenberg, M. Zander and G.
  • hydrocarbon resins can also be described as thermoplastic resins in the sense that they soften when heated and can thus be moulded.
  • the softening point of the hydrocarbon resins is measured according to standard ISO 4625 (“Ring and Ball” method).
  • the Tg is measured according to standard ASTM D3418 (1999).
  • the macrostructure (Mw, Mn and PDI) of the hydrocarbon resin is determined by size exclusion chromatography (SEC); solvent tetrahydrofuran; temperature 35° C.; concentration 1 g/l; flow rate 1 ml/min; solution filtered through a filter with a porosity of 0.45 ⁇ m before injection; Moore calibration with polystyrene standards; set of 3 Waters columns in series (Styragel HR4E, HR1 and HR0.5); detection by differential refractometer (Waters 2410) and its associated operating software (Waters Empower).
  • SEC size exclusion chromatography
  • solvent tetrahydrofuran solvent tetrahydrofuran
  • temperature 35° C. concentration 1 g/l
  • flow rate 1 ml/min solution filtered through a filter with a porosity of 0.45 ⁇ m before injection
  • Moore calibration with polystyrene standards set of 3 Waters columns in series (Styragel HR4E, HR1 and HR0.5
  • the hydrocarbon resins may be aliphatic or aromatic or else of the aliphatic/aromatic type, that is to say based on aliphatic and/or aromatic monomers. They can be natural or synthetic and may or may not be petroleum-based (if such is the case, they are also known under the name of petroleum resins).
  • the hydrocarbon plasticizing resin has a glass transition temperature above 20° C.
  • the hydrocarbon plasticizing resin has at least any one of the following features, more preferentially all of them:
  • the hydrocarbon plasticizing resin is selected from the group consisting of cyclopentadiene homopolymer resins, cyclopentadiene copolymer resins, dicyclopentadiene homopolymer resins, dicyclopentadiene copolymer resins, terpene homopolymer resins, terpene copolymer resins, C5-cut homopolymer resins, C5-cut copolymer resins, C9-cut homopolymer resins, C9-cut copolymer resins, hydrogenated cyclopentadiene homopolymer resins and hydrogenated cyclopentadiene copolymer resins.
  • the hydrocarbon plasticizing resin is a C9-cut copolymer resin or a dicyclopentadiene copolymer resin, which is hydrogenated or non-hydrogenated.
  • a C9-cut copolymer resin or a dicyclopentadiene copolymer resin which is hydrogenated or non-hydrogenated.
  • Hydrocarbon liquid plasticizing agents are known to soften a rubber composition by diluting the elastomer and the reinforcing filler of the rubber composition.
  • Their Tg is typically below ⁇ 20° C., preferentially below ⁇ 40° C.
  • Any hydrocarbon extender oil or any hydrocarbon liquid plasticizing agent for its plasticizing properties with respect to diene elastomers can be used.
  • these plasticizers or these oils which are more or less viscous, are liquids (that is to say, as a reminder, substances which have the ability to eventually take on the shape of their container), as opposed especially to hydrocarbon plasticizing resins which are by nature solid at ambient temperature.
  • hydrocarbon liquid plasticizing agents mention may be made of liquid diene polymers, polyolefin oils, naphthenic oils, paraffinic oils, DAE oils, MES (Medium Extracted Solvate) oils, TDAE (Treated Distillate Aromatic Extract) oils, RAE (Residual Aromatic
  • the hydrocarbon liquid placticizing agent is selected from the group consisting of liquid diene polymers, aliphatic polyolefin oils, paraffinic oils, MES oils, TDAE oils, TRAE oils, SRAE oils, mineral oils and mixtures thereof. More preferentially, the hydrocarbon liquid plasticizing agent is a liquid diene polymer, an aliphatic polyolefin oil, a paraffinic oil, an MES oil or mixtures thereof.
  • the weight ratio between the content of hydrocarbon plasticizing resin and the total content of hydrocarbon plasticizing resin and of hydrocarbon liquid plasticizing agent is greater than 0.4.
  • This particular embodiment is also favourable to improving the handling of a tyre, the tread of which comprises such a rubber composition.
  • the plasticizing system may contain, generally in a small amount, another plasticizing agent other than the hydrocarbon plasticizing resin and the hydrocarbon liquid plasticizing agent useful for the needs of the invention, as long as the desired performance compromise is not detrimentally modified.
  • This other plasticizing agent can be, for example, a processing aid traditionally used in a small amount to promote, for example, the dispersion of the silica.
  • the hydrocarbon plasticizing resin and the hydrocarbon liquid plasticizing agent advantageously represent substantially the main part of the plasticizing system, that is to say the ratio between the content of hydrocarbon plasticizing resin and hydrocarbon liquid plasticizing agent to the content of the total plasticizing system in the rubber composition of the lateral portions, the contents being expressed in phr, is greater than 0.8, very advantageously greater than 0.9.
  • the weight ratio between the content of reinforcing filler and the total content of hydrocarbon plasticizing resin and of hydrocarbon liquid plasticizing agent is greater than or equal to 1.1, and preferably greater than 1.2, the contents being expressed in phr.
  • the composition of the lateral portions according to this particular embodiment provides stiffening within the tread, which makes it possible to improve the handling of a tyre, the tread of which has a high-grip surface due to the use of a highly deformable rubber composition intended to come into contact with the ground.
  • the rubber composition of the lateral portions can also comprise all or some of the usual additives customarily used in elastomer compositions intended for the manufacture of tyres, in particular pigments, protective agents such as anti-ozone waxes, chemical anti-ozonants, antioxidants, a crosslinking system which can be based either on sulfur or on sulfur donors and/or on peroxide and/or on bismaleimides, vulcanization accelerators or retarders, or vulcanization activators.
  • protective agents such as anti-ozone waxes, chemical anti-ozonants, antioxidants, a crosslinking system which can be based either on sulfur or on sulfur donors and/or on peroxide and/or on bismaleimides, vulcanization accelerators or retarders, or vulcanization activators.
  • the actual crosslinking system is preferentially a vulcanization system, that is to say based on sulfur and on a primary vulcanization accelerator.
  • the sulfur is typically provided in the form of molecular sulfur or of a sulfur-donating agent, preferably in molecular form. Sulfur in molecular form is also referred to by the term “molecular sulfur”.
  • sulfur donor means any compound which releases sulfur atoms, optionally combined in the form of a polysulfide chain, which are capable of inserting into the polysulfide chains formed during the vulcanization and bridging the elastomer chains.
  • Various known secondary vulcanization accelerators or vulcanization activators such as zinc oxide, stearic acid, guanidine derivatives (in particular diphenylguanidine), and the like, are added to the vulcanization system, being incorporated during the first non-productive phase and/or during the productive phase.
  • the sulfur content is preferably between 0.5 and 3.0 phr and the content of the primary accelerator is preferably between 0.5 and 5.0 phr.
  • Use may be made, as (primary or secondary) vulcanization accelerator, of any compound that is capable of acting as accelerator of the vulcanization of diene elastomers in the presence of sulfur, notably accelerators of the thiazole type and also derivatives thereof, accelerators of sulfenamide type as regards the primary accelerators, or accelerators of thiuram, dithiocarbamate, dithiophosphate, thiourea and xanthate type as regards the secondary accelerators.
  • primary accelerators examples include sulfenamide compounds such as N-cyclohexyl-2-benzothiazylsulfenamide (“CBS”), N,N-dicyclohexyl-2-benzothiazylsulfenamide (“DCBS”), N-tert-butyl-2-benzothiazylsulfenamide (“TBBS”), and mixtures of these compounds.
  • CBS N-cyclohexyl-2-benzothiazylsulfenamide
  • DCBS N,N-dicyclohexyl-2-benzothiazylsulfenamide
  • TBBS N-tert-butyl-2-benzothiazylsulfenamide
  • the primary accelerator is preferentially a sulfenamide, more preferentially N-cyclohexyl-2-benzothiazylsulfenamide.
  • secondary accelerators examples include thiuram disulfides such as tetraethylthiuram disulfide, tetrabutylthiuram disulfide (“TBTD”), tetrabenzylthiuram disulfide (“TBZTD”) and mixtures of these compounds.
  • the secondary accelerator is preferentially a thiuram disulfide, more preferentially tetrabenzylthiuram disulfide.
  • the crosslinking (or curing), where appropriate the vulcanization, is carried out in a known manner at a temperature generally of between 130° C. and 200° C., for a sufficient time which may vary, for example, between 5 and 90 min, depending especially on the curing temperature, on the crosslinking system adopted and on the crosslinking kinetics of the composition in question.
  • the rubber composition, before crosslinking, may be manufactured in appropriate mixers, using two successive phases of preparation according to a general procedure well known to those skilled in the art: a first phase of thermomechanical working or kneading (sometimes referred to as a “non-productive” phase) at high temperature, up to a maximum temperature of between 110° C. and 190° C., preferably between 130° C. and 180° C., followed by a second phase of mechanical working (sometimes referred to as a “productive” phase) at lower temperature, typically below 110° C., for example between 40° C. and 100° C., during which finishing phase the sulfur or the sulfur donor and the vulcanization accelerator are incorporated.
  • a first phase of thermomechanical working or kneading sometimes referred to as a “non-productive” phase
  • a second phase of mechanical working sometimes referred to as a “productive” phase
  • the first (non-productive) phase is carried out in a single thermomechanical step during which all the necessary constituents, the optional additional processing aids and various other additives, with the exception of the crosslinking system, are introduced into an appropriate mixer, such as a normal internal mixer.
  • the total duration of the kneading, in this non-productive phase is preferably between 1 and 15 min.
  • the rubber composition can be calendered or extruded in the form of a sheet or of a slab, in particular for a laboratory characterization, or also in the form of a rubber semi-finished product (or profiled element) that can be used in a tyre.
  • the composition may be either in the raw state (before crosslinking or vulcanization) or in the cured state (after crosslinking or vulcanization), may be a semi-finished product which can be used in a tyre.
  • the microstructure of the elastomers is determined by 1 H NMR analysis, compensated for by the 13 C NMR analysis when the resolution of the 1 H NMR spectra does not make it possible to assign and quantify all the entities.
  • the measurements are performed using a Brüker 500 MHz NMR spectrometer at frequencies of 500.43 MHz for proton observation and 125.83 MHz for carbon observation.
  • a 4 mm z-grad HRMAS probe is used for proton and carbon observation in proton-decoupled mode.
  • the spectra are acquired at rotational speeds of from 4000 Hz to 5000 Hz.
  • the preparation of the insoluble samples is performed in rotors filled with the analysed material and a deuterated solvent enabling swelling, generally deuterated chloroform (CDCl3).
  • a deuterated solvent enabling swelling generally deuterated chloroform (CDCl3).
  • the solvent used must always be deuterated and its chemical nature may be adapted by those skilled in the art.
  • the amounts of material used are adjusted so as to obtain spectra of sufficient sensitivity and resolution.
  • the soluble samples are dissolved in a deuterated solvent (about 25 mg of elastomer in 1 mL), generally deuterated chloroform (CDCl3).
  • a deuterated solvent about 25 mg of elastomer in 1 mL
  • deuterated chloroform CDCl3
  • the solvent or solvent blend used must always be deuterated and its chemical nature may be adapted by those skilled in the art.
  • a 30° single pulse sequence is used for proton NMR.
  • the spectral window is set to observe all of the resonance lines belonging to the analysed molecules.
  • the number of accumulations is set so as to obtain a signal-to-noise ratio that is sufficient for quantification of each unit.
  • the recycle delay between each pulse is adapted to obtain a quantitative measurement.
  • a 30° single pulse sequence is used for carbon NMR, with proton decoupling only during the acquisition to avoid nuclear Overhauser effects (NOE) and to remain quantitative.
  • the spectral window is set to observe all of the resonance lines belonging to the analysed molecules.
  • the number of accumulations is set so as to obtain a signal-to-noise ratio that is sufficient for quantification of each unit.
  • the recycle delay between each pulse is adapted to obtain a quantitative measurement.
  • the NMR measurements are performed at 25° C.
  • the evaluation of the stiffness of the rubber compositions was evaluated by determining the dynamic shear modulus G*.
  • the response of a sample of vulcanized composition subjected to a sinusoidal alternating shear stress at an imposed stress of 0.7 MPa and at a frequency of 10 Hz, during a temperature sweep, at a minimum temperature below the Tg of the elastomers of the compositions up to a maximum temperature above 100° C. is recorded; the values of G* are taken at the temperature of 60° C.
  • the elastomers, the reinforcing fillers and the various other ingredients, with the exception of the sulfur and the vulcanization accelerator, are successively introduced into an internal mixer (final degree of filling: approximately 70% by volume), the initial vessel temperature of which is about 80° C.
  • Thermomechanical working (non-productive phase) is then performed in one step, which lasts in total approximately 3 to 4 min, until a maximum “dropping” temperature of 165° C. is reached.
  • the mixture thus obtained is recovered and cooled, and sulfur and the vulcanization accelerator are then incorporated on a mixer (homofinisher) at 30° C., the whole being kneaded (productive phase) for an appropriate time (for example approximately ten minutes).
  • compositions thus obtained are then calendered either in the form of slabs (thickness 2 to 3 mm) or of thin sheets of rubber for the measurement of their physical or mechanical properties, or extruded to form for example a profiled element for a tyre.
  • Table 1 below describes a rubber composition T1 from the prior art, used as a mixture of the central portion of the tread, and also five compositions in accordance with the invention for mixtures of the lateral portions.
  • the five rubber compositions M1 to M5 all contain a copolymer of ethylene and of 1,3-butadiene in which the content of ethylene units is greater than 50%.
  • the copolymer bears a silanol or alkoxysilane function at the chain end.
  • the copolymer of ethylene and of 1,3-butadiene (EBR) used in the compositions M1 to M4 is prepared according to the following procedure:
  • the cocatalyst, the butyloctylmagnesium (BOMAG) (0.00021 mol/l) and then the metallocene [ ⁇ Me 2 SiFlu 2 Nd( ⁇ -BH 4 ) 2 Li(THF) ⁇ 2 ] (0.07 mol/l) are added to a reactor containing methylcyclohexane, the Flu symbol representing the C 13 H 8 group.
  • the alkylation time is 10 minutes, the reaction temperature is 20° C.
  • the monomers in the form of a gas mixture of ethylene/1,3-butadiene molar composition: 80/20 are added continuously.
  • the polymerization is carried out under conditions of constant temperature and pressure of 80° C. and 8 bar.
  • the polymerization reaction is stopped by cooling, degassing of the reactor and addition of ethanol.
  • An antioxidant is added to the polymer solution.
  • the copolymer is recovered by drying in an oven under vacuum to constant weight.
  • the molar content of ethylene units is 79%
  • the molar content of 1,4 units is 6%
  • the molar content of 1,2 units is 8%
  • the molar content of 1,2-cyclohexanediyl units is 7%.
  • the Mooney viscosity is 85.
  • the copolymer is prepared according to the same procedure as the EBR copolymer, with one difference which is as follows:
  • the content of the reactor is degassed and then the functionalizing agent, (N,N-dimethyl-3-aminopropyl)methyldimethoxysilane, is introduced under an inert atmosphere by excess pressure.
  • the reaction medium is stirred for a time of 15 minutes and a temperature of 80° C. After reaction, the medium is degassed and then precipitated from methanol.
  • the polymers are redissolved in toluene, then precipitated from methanol so as to eliminate the ungrafted “silane” molecules, which makes it possible to improve the quality of the signals of the spectra for the quantification of the function content and the integration of the various signals.
  • the polymer is treated with antioxidant then dried at 60° C. under vacuum to constant weight.
  • the molar content of ethylene units is 76%
  • the molar content of 1,4 units is 6%
  • the molar content of 1,2 units is 9%
  • the molar content of 1,2-cyclohexanediyl units is 9%.
  • the Mooney viscosity is 84.
  • Table 2 below shows the values of the ratio between the filler content and the plasticizing system content.
  • Table 3 above describes a rubber composition T1 from the prior art, used as a mixture of the central portion of the tread, and also five compositions in accordance with the invention for mixtures capable of constituting the lateral tread portions.
  • the rubber composition T1 comprises 100 phr of SBR and has a dynamic shear modulus of 0.9 MPa, which makes this composition suitable for providing the tyre with excellent grip due in particular to a high contact area on rough ground.
  • composition M1 to M4 in accordance with the invention for the lateral tread portions comprise 100 phr of the EBR diene elastomer described above and composition M5 comprises 100 phr of the EBR-F diene elastomer as described above.
  • compositions have a dynamic shear modulus of between 1.2 and 2.3 MPa, which makes them suitable for stiffening the tread and thus improving the handling of the tyre, while allowing their use in contact with a ground on which it is running, when the tyre tread is new and worn.
  • composition T1 the filler contents of these compositions are much lower than those of composition T1, which allows a significant reduction in their hysteresis.

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US17/416,654 2018-12-21 2019-12-10 Tread for a tire Pending US20220073713A1 (en)

Applications Claiming Priority (3)

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FR1873881A FR3090656A3 (fr) 2018-12-21 2018-12-21 Bande de roulement pour pneumatique
FRFR1873881 2018-12-21
PCT/FR2019/052998 WO2020128226A1 (fr) 2018-12-21 2019-12-10 Bande de roulement pour pneumatique

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USD958053S1 (en) * 2020-07-03 2022-07-19 Bridgestone Corporation Motorcycle tire
USD960079S1 (en) * 2020-08-03 2022-08-09 Ceat Limited Tire
USD967000S1 (en) * 2020-06-22 2022-10-18 Compagnie Generale Des Etablissements Michelin Tire
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US11731401B2 (en) 2019-12-17 2023-08-22 Compagnie Generale Des Etablissements Michelin Elastomer laminate
EP4353495A1 (en) * 2022-10-14 2024-04-17 Sumitomo Rubber Industries, Ltd. Tire
US12371523B2 (en) 2019-12-17 2025-07-29 Compagnie Generale Des Etablissements Michelin Rubber composition
USD1096595S1 (en) 2023-06-29 2025-10-07 Compagnie Generale Des Etablissements Michelin Tire
US12594745B2 (en) 2021-03-11 2026-04-07 Compagnie Generale Des Etablissements Michelin Elastomer laminate
US12600843B2 (en) 2021-03-11 2026-04-14 Compagnie Generale Des Etablissements Michelin Elastomer composition
USD1126130S1 (en) 2024-02-27 2026-05-12 Compagnie Generale Des Etablissements Michelin Tire

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12371523B2 (en) 2019-12-17 2025-07-29 Compagnie Generale Des Etablissements Michelin Rubber composition
US11731401B2 (en) 2019-12-17 2023-08-22 Compagnie Generale Des Etablissements Michelin Elastomer laminate
USD967000S1 (en) * 2020-06-22 2022-10-18 Compagnie Generale Des Etablissements Michelin Tire
USD967750S1 (en) * 2020-06-22 2022-10-25 Compagnie Generale Des Etablissements Michelin Tire
USD958054S1 (en) * 2020-07-03 2022-07-19 Bridgestone Corporation Motorcycle tire
USD958053S1 (en) * 2020-07-03 2022-07-19 Bridgestone Corporation Motorcycle tire
USD958055S1 (en) * 2020-07-09 2022-07-19 Bridgestone Corporation Motorcycle tire
USD960079S1 (en) * 2020-08-03 2022-08-09 Ceat Limited Tire
US12594745B2 (en) 2021-03-11 2026-04-07 Compagnie Generale Des Etablissements Michelin Elastomer laminate
US12600843B2 (en) 2021-03-11 2026-04-14 Compagnie Generale Des Etablissements Michelin Elastomer composition
EP4353495A1 (en) * 2022-10-14 2024-04-17 Sumitomo Rubber Industries, Ltd. Tire
USD1096595S1 (en) 2023-06-29 2025-10-07 Compagnie Generale Des Etablissements Michelin Tire
USD1126130S1 (en) 2024-02-27 2026-05-12 Compagnie Generale Des Etablissements Michelin Tire

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EP3898265B1 (fr) 2023-02-08
WO2020128226A1 (fr) 2020-06-25
FR3090660A1 (fr) 2020-06-26
FR3090656A3 (fr) 2020-06-26
CN113195247A (zh) 2021-07-30
JP2022514717A (ja) 2022-02-14
JP7470122B2 (ja) 2024-04-17

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